Thermoplastic particulates coated with polymer nanoparticles and methods for production and use thereof

ABSTRACT

Additive manufacturing processes featuring consolidation of thermoplastic particulates may form printed objects in a range of shapes. Inorganic nanoparticles disposed upon the outer surface of the thermoplastic particulates may improve flow performance of the thermoplastic particulates during additive manufacturing, but may be undesirable to incorporate in some printed objects. Polymer nanoparticles may be substituted for inorganic nanoparticles in some instances to address this difficulty and provide other advantages. Particulate compositions suitable for additive manufacturing may comprise: a plurality of thermoplastic particulates comprising a thermoplastic polymer and a plurality of polymer nanoparticles disposed upon an outer surface of the thermoplastic particulates, the polymer nanoparticles comprising a crosslinked fluorinated polymer.

CROSS-REFERENCE TO RELATED APPLICATIONS

Not applicable.

FIELD

The present disclosure generally relates to additive manufacturing, moreparticularly additive manufacturing processes featuring consolidation ofpowder particulates coated with nanoparticles.

BACKGROUND

Additive manufacturing, also known as three-dimensional (3-D) printing,is a rapidly growing technology area. Although additive manufacturinghas traditionally been used for rapid prototyping activities, thistechnique is being increasingly employed for producing commercial andindustrial parts (printed objects) in any number of complex shapes.Additive manufacturing processes operate by layer-by-layer deposition ofeither 1) a stream of molten printing material or a liquid precursor toa printing material, or 2) powder particulates of a printing material.The layer-by-layer deposition usually takes place under control of acomputer to deposit and consolidate the printing material in preciselocations based upon a digital three-dimensional computer-aided designmodel (“blueprint”) of the part to be manufactured. Powder bed fusion(PBF) of powder particulates is an especially beneficial additivemanufacturing method. In a particular example, consolidation of powderparticulates may take place in a powder bed deposited layer-by-layerusing a three-dimensional printing system that employs a laser orelectron beam to heat precise locations of the powder bed, therebyconsolidating specified powder particulates to form a part having apredetermined shape. Selective laser sintering (SLS) represents aparticular example of a process suitable for promoting localizedconsolidation of powder particulates during powder bed fusion to form apart in a desired shape. Other localized heating techniques forparticulate consolidation that may be similarly employed include, forexample, electron beam melting (EBM), binder jetting, multi-jet fusion(MJF), and selective heat melting (SHM).

Among the powder particulates suitable for use in three-dimensionalprinting are those comprising thermoplastic polymers. Although a widearray of thermoplastic polymers are known, there are relatively fewhaving properties compatible for use in current three-dimensionalprinting techniques employing particulate consolidation. Thermoplasticpolymers suitable for undergoing particulate consolidation into partsmay include those having a significant difference between the onset ofmelting and the onset of crystallization, which may promote goodstructural and mechanical integrity following directed heating topromote particulate consolidation. Ready formation of particulatessuitable for undergoing deposition in a powder bed is anothersignificant consideration.

For satisfactory printing performance to be realized, thermoplasticparticulates need to maintain good flow properties in the solid state.Flow properties may be evaluated, for example, by measuring the fractionof thermoplastic particulates from a sample that are able to passthrough a standard sieve of a specified size and/or by measuring of theangle of repose. High fractions of sievable thermoplastic particulatesmay be indicative of the thermoplastic particulates existing asnon-agglomerated, substantially individual particulates, which may becharacteristic of ready powder flow. Lower values of the angle ofrepose, in contrast, may be characteristic of ready powder flow. Arelatively narrow particle size distribution and regularity of theparticulate shape in a sample may also facilitate good powder flowperformance. Substantial absence of particulate fines may also bedesirable for promoting powder flow.

Thermoplastic particulates are oftentimes obtained commercially bycryogenic grinding or precipitation processes, which may result inirregular particulate shapes and wide particle size distributions.Irregular particulate shapes and wide particle size distributions mayalso result in poor powder flow performance, as well as extensive voidformation during three-dimensional printing processes. Poor powder flowperformance may be addressed to some degree through dry blending withfillers and flow aids, but these additives may have limitedeffectiveness with softer polymer materials, such as elastomers, due toparticulate aggregation. In addition, fillers and flow aids may beundesirable to incorporate in printed objects in some instances.

Void formation resulting from irregular particulate shapes may be moredifficult to address. Extensive void formation during particulateconsolidation may significantly decrease the ultimate material strengthof a printed object compared to that otherwise obtainable throughcasting or machining of the same thermoplastic polymer. Therefore, itcan be desirable for good flow performance to be realized oncethermoplastic particulates have been liquefied in order to promoteadequate particulate consolidation with limited void formation.

Thermoplastic particulates may also be formed by melt emulsificationprocesses, such as those described in U.S. Pat. No. 4,863,646, which isincorporated herein by reference in its entirety. In melt emulsificationprocesses, a thermoplastic polymer is dispersed as liquefied droplets ina carrier fluid, in which the thermoplastic polymer has no or minimalsolubility above the polymer's melting point or softening temperature.Upon cooling the liquefied droplets below the melting point or softeningtemperature, thermoplastic particulates having a substantially sphericalshape may be formed, albeit with a wide particle size distribution. Assuch, the thermoplastic particulates produced in conventional meltemulsification processes may remain non-ideally suited forthree-dimensional printing processes.

The particle size distribution of thermoplastic particulates formedduring melt emulsification can be narrowed significantly byincorporating a plurality of nanoparticles into the carrier fluid, asdescribed in U.S. patent application Ser. No. 16/946,622, filed on Jun.30, 2020 and incorporated herein by reference. Various types of silicananoparticles and other inorganic nanoparticles may be particularlydesirable in this regard. Thermoplastic particulates formed in thismanner may feature at least a partial coating of nanoparticles upon theparticulate surface, wherein the nanoparticles are robustly adhered toand/or embedded in the particulate surface. The adhered/embeddednanoparticles may promote much better powder flow performance than thatobtained when dry blending a flow aid with uncoated thermoplasticparticulates. The narrow particle size distribution of thermoplasticparticulates having a nanoparticle coating thereon may allow readysintering with a manageable amount of void formation to be realized inmany instances. Although a wide range of printed objects may be formedsatisfactorily with silica-coated thermoplastic particulates, there arecertain instances where incorporation of silica or other inorganicnanoparticles in a printed object may be undesirable. For example,excessive silica or inorganic nanoparticles may compromise themechanical performance of a printed object in some instances. Polymernanoparticles may be a satisfactory replacement for silica and otherinorganic nanoparticles, but there are few types of polymernanoparticles that are readily formable, are compatible with meltemulsification conditions, and promote good flow performance and limitvoid formation during additive manufacturing.

SUMMARY

The present disclosure provides particulate compositions suitable foradditive manufacturing. The particulate compositions comprise: aplurality of thermoplastic particulates comprising a thermoplasticpolymer, and a plurality of polymer nanoparticles disposed upon an outersurface of the thermoplastic particulates, the polymer nanoparticlescomprising a crosslinked fluorinated polymer.

The present disclosure also provides methods for forming consolidatedparts using the particulate compositions. The methods comprise:providing a particulate composition comprising a plurality ofthermoplastic particulates comprising a thermoplastic polymer, and aplurality of polymer nanoparticles disposed upon an outer surface of thethermoplastic particulates, the polymer nanoparticles comprising acrosslinked fluorinated polymer; depositing the particulate compositionlayer-by-layer in a powder bed; and heating a portion of the powder bedto consolidate a portion of the thermoplastic particulates into aconsolidated part having a specified shape. The consolidated parts maycomprise a thermoplastic matrix formed by consolidation of thermoplasticparticulates; and polymer nanoparticles admixed with the thermoplasticmatrix.

The present disclosure also provides methods for forming particulatecompositions suitable for additive manufacturing. The methods comprise:combining a thermoplastic polymer and polymer nanoparticles with acarrier fluid at a heating temperature at or above a melting point orsoftening temperature of the thermoplastic polymer and below a meltingpoint, softening temperature or decomposition temperature of the polymernanoparticles; wherein the thermoplastic polymer and the polymernanoparticles are substantially immiscible in the carrier fluid at theheating temperature, and the polymer nanoparticles comprise acrosslinked fluorinated polymer; applying sufficient shear to dispersethe thermoplastic polymer as liquefied droplets in the carrier fluid atthe heating temperature in the presence of the polymer nanoparticles;after liquefied droplets have formed, cooling the carrier fluid to atleast a temperature at which thermoplastic particulates in a solidifiedstate form, the thermoplastic particulates comprising the thermoplasticpolymer and at least a portion of the polymer nanoparticles disposedupon an outer surface of the thermoplastic particulates; and separatingthe thermoplastic particulates from the carrier fluid.

BRIEF DESCRIPTION OF THE DRAWINGS

The following figures are included to illustrate certain aspects of thepresent disclosure, and should not be viewed as exclusive embodiments.The subject matter disclosed is capable of considerable modifications,alterations, combinations, and equivalents in form and function, as willoccur to one having ordinary skill in the art and having the benefit ofthis disclosure.

FIG. 1 is a flow chart of a non-limiting example method for producingthermoplastic particulates in accordance with the present disclosure.

FIG. 2 is a scanning electron microscope image of the polyurethaneparticulates prepared in accordance with Example 1.

FIG. 3 is a graph showing the particle size distribution of thepolyurethane particulates prepared in accordance with Example 1.

FIG. 4 is a scanning electron microscope image of the polyamideparticulates prepared in accordance with Example 4.

FIG. 5 is a graph showing the particle size distribution of thepolyamide particulates prepared in accordance with Example 4.

DETAILED DESCRIPTION

The present disclosure generally relates to additive manufacturing, moreparticularly additive manufacturing processes featuring consolidation ofpowder particulates having enhanced sintering properties.

As discussed above, thermoplastic particulates comprising athermoplastic polymer may be suitable for use in three-dimensionalprinting processes, particularly those employing selective lasersintering and similar processes to consolidate specified locations of apowder bed to form a part having a predetermined shape. Commerciallysourced thermoplastic particulates presently may be obtained inirregular shapes and/or with wide particle size distributions, which maylead to poor flow performance and/or incomplete particulateconsolidation during printing. Melt emulsification processes employingsilica and other inorganic nanoparticles during thermoplasticparticulate formation may afford thermoplastic particulates having highsphericity and narrow particle size distributions, which may affordimproved powder flow performance and particulate consolidationproperties. Although silica and other inorganic nanoparticles usuallymay be suitably incorporated into printed objects, there are certaininstances in which incorporation of such nanoparticles may beunfavorable or lead to ineffective particulate consolidation. There maybe a small concentration window effective for incorporating silica orother inorganic nanoparticles in thermoplastic particulates in asuitable amount for forming a desired particle size range while stillallowing effective particulate consolidation to take place. Accordingly,it may be very difficult in some cases to strike a balance betweenadequate powder flow performance and good liquid flow performance whenconsolidating thermoplastic powder particulates stabilized with silicaor other inorganic nanoparticles.

Polymer nanoparticles may represent a suitable substitute for silica andother inorganic nanoparticles, since polymer nanoparticles may be morereadily compatible with the polymer matrix of a printed object followingparticulate consolidation. However, there are comparatively few types ofpolymer nanoparticles that may be suitably formed and subsequentlyisolated (e.g., as a latex emulsion, followed by isolation of theemulsion particles), are compatible with melt emulsification conditions(e.g., polymers that are insoluble in a melt emulsification carrierfluid and do not melt or decompose up to the melt emulsificationtemperature employed), and are capable of effectively promoting powderflow to limit void formation during particulate consolidation. Accordingto the present disclosure, crosslinked fluorinated polymers,particularly crosslinked fluorinated acrylic polymers, may surprisinglyfulfill all of these desirable attributes, as discussed in furtherdetail below. A wide range of compositional diversity may beaccommodated in crosslinked fluorinated acrylic polymers, includingincorporation of non-fluorinated ethylenically unsaturated monomersand/or varying the crosslinking density to promote tailoring of thephysical properties of the polymer nanoparticles.

Both crosslinking and fluorination are believed to be desirable forfacilitating compatibility with melt emulsification conditions accordingto the disclosure herein. For example, crosslinked acrylic polymers thatare non-fluorinated may undergo decomposition at a temperature belowthat commonly employed during melt emulsification, thereby precludingtheir ability to promote stabilization of thermoplastic particulates.Non-crosslinked polymers may similarly undergo decomposition and/or meltat the temperatures commonly employed during melt emulsification. Whilevarious fluorinated polymers having high thermal stability are known(e.g., polytetrafluoroethylene), effective emulsification techniques forproducing these types of polymers in nanoparticle form are not believedto be known at present.

In some instances, a combination of crosslinked fluorinated polymernanoparticles and silica nanoparticles or other inorganic nanoparticlesmay be employed in the disclosure herein. For example, the crosslinkedfluorinated polymer nanoparticles may be used in an effective amount todecrease the amount of silica or inorganic nanoparticles to a level thatremains effective during melt emulsification but does not becomeproblematic during particulate consolidation. Such approaches may bemore cost-effective than complete replacement of silica or inorganicnanoparticles with crosslinked fluorinated polymer nanoparticles, asdiscussed herein. It is to be appreciated, however, that completereplacement of silica or other inorganic nanoparticles with polymernanoparticles may be more desirable in some instances.

Terms used in the description and claims herein have their plain andordinary meaning, except as modified by the paragraphs below.

As used herein, the term “thermoplastic polymer” refers to a polymermaterial that softens and hardens reversibly on heating and coolingabove a specified temperature (e.g., melting point, softening point,glass transition temperature, or the like). Thermoplastic polymersencompass both elastomeric and non-elastomeric thermoplastic polymers.

As used herein, the term “polymer” refers to an oligomeric materialformed from one or more organic monomers.

As used herein, the term “nanoparticle” refers to a particulate materialhaving a particle size ranging from about 1 nm to about 500 nm.

As used herein, the term “oxide” refers to both metal oxides andnon-metal oxides. For purposes of the present disclosure, silicon isconsidered to be a metal.

As used herein, the term “oxide nanoparticles” refers to a particulatematerial having a particle size ranging from about 1 nm to about 500 nmand comprising a metal oxide or a non-metal oxide.

As used herein, the term “inorganic nanoparticles” refers to anynanoparticles that are not polymer nanoparticles.

As used herein, the term “associated” refers to chemical bonding,physical admixture with a matrix, or physical adherence to a surface.

As used herein, the terms “admixed,” “admixture” or like related termsrefer to dissolution of a first substance in a second substance ordispersion of a first substance as a solid in a second substance,wherein the dispersion may be uniform or non-uniform.

As used herein, the term “D₁₀” refers to a diameter at which 10% of thesample (on a volume basis unless otherwise specified) is comprised ofparticles having a diameter less than said diameter value. As usedherein, the term “D₅₀” refers to a diameter at which 50% of the sample(on a volume basis unless otherwise specified) is comprised of particleshaving a diameter less than said diameter value. D₅₀ may also bereferred to as the “average particle size.” As used herein, the term“D₉₀” refers to a diameter at which 90% of the sample (on a volume basisunless otherwise specified) is comprised of particles having a diameterless than said diameter value.

As used herein, the terms “diameter span,” “span” and “span size”provide an indication of the breadth of a particle size distribution andis calculated as (D₉₀−D₁₀)/D₅₀ (again, each D-value is based on volume,unless otherwise specified).

As used herein, the term “shear” refers to stirring or a similar processthat induces mechanical agitation in a fluid.

As used herein, the term “embed” relative to nanoparticles and a surfaceof a thermoplastic particulate refers to the nanoparticles being atleast partially extended into the surface such that polymer is incontact with the nanoparticles to a greater degree than would occur ifthe nanoparticles were simply laid on the surface, thereby contactingthe surface tangentially.

As used herein, the terms “circularity” and “sphericity” refer to howclose a particulate or a plurality of particulates is to a perfectsphere. To determine circularity, optical microscopy images are taken ofthe particulates. The perimeter (P) and area (A) of a particulate in theplane of the microscopy image is calculated (e.g., using a SYSMEX FPIA3000 particle shape and particle size analyzer, available from MalvernInstruments). The circularity of a particulate is C_(EA)/P, where C_(EA)is the circumference of a circle having the area equivalent to the area(A) of the actual particulate.

As used herein, the viscosity of carrier fluids refer to the kinematicviscosity at 25° C., unless otherwise specified, and are measured perASTM D445-19, unless otherwise specified.

The melting point of a thermoplastic polymer herein, unless otherwisespecified, is determined by ASTM E794-06(2018) with 10° C./min rampingand cooling rates.

The softening temperature or softening point of a thermoplastic polymerherein, unless otherwise specified, is determined by ASTM D6090-17. Thesoftening temperature can be measured by using a cup and ball apparatusavailable from Mettler-Toledo using a 0.50 gram sample with a heatingrate of 1° C./min.

As used herein, the term “fluorinated” refers to a polymer or a monomerunit thereof that contains at least one fluorine atom covalently bondedthereto.

As used herein, the term “perfluorinated” refers to a polymer or amonomer unit thereof having all available hydrogen atoms of a particulartype substituted with fluorine atoms.

As used herein, the term “crosslinked” refers to a polymeric materialhaving a group covalently bridging between two different monomer units.Crosslinking may be internal within a given polymer chain(intramolecular), between two or more different polymer chains(intermolecular), or any combination thereof.

As used herein, the term “(meth)acrylic monomer” refers to a family ofmonomers comprising acrylic acid, methacrylic acid, or a derivative formthereof. Suitable derivative forms of (meth)acrylic monomers may includeesters or amides. Thus, for any particular (meth)acrylic monomerdisclosed herein, both the acrylic and methacrylic forms are expresslydisclosed.

As used herein, the terms “latex,” “latex emulsion” and “latexdispersion” refer equivalently to an aqueous emulsion comprisingemulsified polymer particulates.

Accordingly, particulate compositions of the present disclosure maycomprise a plurality of thermoplastic particulates comprising athermoplastic polymer, and a plurality of polymer nanoparticles disposedupon an outer surface of the thermoplastic particulates. The polymernanoparticles comprise a crosslinked fluorinated polymer, suitableexamples of which are discussed in further detail below.

Suitable crosslinked fluorinated polymers may comprise at least onefluorinated monomer and at least one crosslinking agent, at least onenon-fluorinated monomer and at least one fluorinated crosslinking agent,at least one fluorinated monomer and at least one fluorinatedcrosslinking agent, or any combination thereof. Particularly suitablecrosslinked fluorinated polymers may be formed through polymerization ofat least one ethylenically unsaturated monomer, especially a(meth)acrylic monomer, and at least one crosslinking agent bearing twoor more ethylenic unsaturations. At least one of the at least oneethylenically unsaturated monomer and the at least one crosslinkingagent may be fluorinated. More specific examples of suitable crosslinkedfluorinated polymers may include those formable through emulsionpolymerization, which may allow the fluorinated crosslinked polymer tobe readily isolated as polymer nanoparticles following solvent removalfrom the emulsion (e.g., through spray drying). Suitable emulsionpolymerization reaction conditions are specified in more detail below.

More specific examples of crosslinked fluorinated polymers suitable forforming polymer nanoparticles may comprise a fluorinated (meth)acrylicmonomer, particularly a fluorinated (meth)acrylic ester monomer, and adivinyl crosslinker. 2,2,2-Trifluoromethyl (meth)acrylate anddivinylbenzene represent an illustrative pairing of fluorinated(meth)acrylic monomer and divinyl crosslinker. Some or other examples ofcrosslinked fluorinated polymers may comprise a fluorinated(meth)acrylic monomer including, but not limited to, pentafluorophenyl(meth)acrylate, 2,4,6-trifluorophenyl (meth)acrylate,2,2,3,3,3-pentafluoropropyl (meth)acrylate, perfluoropropyl(meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate,perfluoroisopropyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate,2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate,2,2,3,3,4,4-hexafluorobutyl (meth)acrylate, 2,2,3,4,4,4-hexafluorobutyl(meth)acrylate, perfluorobutyl (meth)acrylate,2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate,2,2,3,3,4,4,5,5,5-nonafluoropentyl (meth)acrylate, perfluoropentyl(meth)acrylate, 3,3,4,4,5,5,6,6,6-nonafluorohexyl (meth)acrylate,2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl (meth)acrylate,3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth)acrylate,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptafluorodecyl (meth)acrylate,octafluoropentyl (meth)acrylate,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12-heneicosafluorododecyl(meth)acrylate,2-[1′,1′,1′-tifluoro-2′-(trifluoromethyl)-2′-hydroxy)propyl]-3-norbornyl(meth)acrylate, perfluorocyclohexyl (meth)acrylate,1H,1H,2H,2H-heptadecafluorodecyl methacrylate, 2,2,3,3-tetrafluoropropyl(meth)acrylate,2-[(1′,1′,1′-trifluoro-2′-(trifluoromethyl)-2′-hydroxy)propyl]-3-norbornyl(meth)acrylate, any combination thereof, and the like. The correspondingamide forms of the foregoing (meth)acrylic monomers may be employed insome instances.

Any of the foregoing fluorinated (meth)acrylic monomers may becrosslinked with a divinyl crosslinker, such as divinylbenzene or othersuitable crosslinker containing at least two vinyl groups. Crosslinkerssuitable for promoting crosslinking of ethylenically unsaturatedmonomers, particularly fluorinated (meth)acrylic monomers, may include,but are not limited to, diethyleneglycol di(meth)acrylate,triethyleneglycol di(meth)acrylate, tetraethyleneglycoldi(meth)acrylate, polyethyleneglycol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, neopentylglycol di(meth)acrylate, tripropyleneglycoldi(meth)acrylate, polypropyleneglycol di(meth)acrylate,2,2′-bis(4-((meth)acryloxy/diethoxy)phenyl)propane, trimethylolpropanetri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate,1,3-butyleneglycol di(meth)acrylate, neopentylglycol di(meth)acrylate,polypropyleneglycol di(meth)acrylate,2,2′-bis(4-((meth)acryloxy/polyethoxy)phenyl)propane, divinylbenzene,divinylnaphthalene, divinyl ether, any combination thereof, and thelike. Dienes such as 1,3-butadiene and isoprene may comprise a suitablecrosslinker in some instances.

In addition, the crosslinker may be fluorinated to produce a suitablecrosslinked fluorinated polymer. A fluorinated crosslinker may beutilized to crosslink a fluorinated polymer (e.g., a polymer comprisinga fluorinated monomer, such as a fluorinated (meth)acrylic monomer) or apolymer that is otherwise unfluorinated. Suitable fluorinatedcrosslinking agents may include fluorinated divinyl crosslinking agentssuch as, for example, 1,8-divinylperfluorooctane,1,6-divinylperfluorohexane, and 1,4-divinylperfluorobutane.

The mole ratio of the crosslinker containing at least two vinyl groups,such as divinylbenzene, may be chosen to provide a desired crosslinkingdensity in the crosslinked fluorinated polymers disclosed herein. Thecrosslinking density may be selected to alter the melting point ordecomposition temperature of the polymer nanoparticles, for example. Innon-limiting examples, the crosslinker, such as a divinyl crosslinker,may be present in an amount ranging from about 1 mol. % to about 50 mol.% relative to total monomers undergoing polymerization to form polymernanoparticles according to the disclosure herein. In more specificinstances, the amount of crosslinker may range from about 1 mol. % toabout 10 mol. %, or about 10 mol. % to about 25 mol. %, or about 25 mol.% to about 40 mol. %, or about 40 mol. % to about 50 mol. %.

Commercial divinylbenzene may contain up to about 30 wt. %divinylbenzene and up to about 50 wt. % ethylvinylbenzene.Ethylvinylbenzene does not contain two vinyl groups to promotecrosslinking, but it may undergo copolymerization with an ethylenicallyunsaturated monomer, such as the fluorinated (meth)acrylic monomersspecified above. As such, particular fluorinated crosslinked polymers ofthe present disclosure may comprise fluorinated (meth)acrylic monomerscopolymerized with ethylvinylbenzene monomers, wherein at least aportion of the fluorinated (meth)acrylic monomers and/or theethylvinylbenzene monomers are further crosslinked with divinylbenzene.

Accordingly, the crosslinked fluorinated polymers of the presentdisclosure, such as a crosslinked fluorinated polymer comprising afluorinated (meth)acrylic monomer and a divinylbenzene crosslinker, mayfurther comprise an ethylenically unsaturated co-monomer differing fromthe fluorinated (meth)acrylic monomer. The ethylenically unsaturatedco-monomer may be fluorinated or non-fluorinated. The ethylenicallyunsaturated co-monomer may be ethylvinylbenzene in some embodiments.

Other suitable examples of ethylenically unsaturated monomers that mayundergo copolymerization with a fluorinated (meth)acrylic monomer and adivinyl crosslinker are not considered to be particularly limited,provided that polymer nanoparticles may be formed therefrom throughemulsion polymerization. Suitable ethylenically unsaturated co-monomersmay include, for example, (meth)acrylamide monomers,amine-functionalized (meth)acrylate monomers, polyether-functionalized(meth)acrylate monomers, and the like. Specific examples of suitableco-monomers may include, for instance, n-butyl (meth)acrylate, isobutyl(meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate,2-ethylhexyl (meth)acrylate, and cycloalkyl (meth)acrylates such asisobornyl (meth)acrylate and cyclohexyl (meth)acrylate,(meth)acrylamide, hydroxy-functionalized (meth)acrylate monomers such ashydroxyethyl (meth)acrylate and hydroxylpropyl (meth)acrylate, and(meth)acrylamide derivatives such as N-methylol (meth)acrylamide anddiacetone (meth)acrylamide.

Other suitable ethylenically unsaturated monomers that may be present inthe crosslinked fluorinated polymers disclosed herein may include atleast one amine group, which may be a primary amine, a secondary amineor a tertiary amine. Particularly suitable examples of ethylenicallyunsaturated monomers comprising at least one amine group include(meth)acrylate monomers such as, for example, 2-(dimethylamino)ethyl(meth)acrylate, 3-(dimethylamino)propyl (meth)acrylate,2-(diethylamino)ethyl (meth)acrylate, 3-(diethylamino)propyl(meth)acrylate, 2-(ethylamino)ethyl (meth)acrylate, 3-(ethylamino)propyl(meth)acrylate, 2-(methylamino)ethyl (meth)acrylate,3-(methylamino)propyl (meth)acrylate, 2-(tert-butylamino)ethyl(meth)acrylate, 3-(tert-butylamino)propyl (meth)acrylate,2-(dimethylamino)ethyl (meth)acrylamide, 3-(dimethylamino)propyl(meth)acrylamide, 2-(diethylamino)ethyl (meth)acrylamide,3-(dimethylamino)propyl (meth)acrylamide, 2-(methylamino)ethyl(meth)acrylamide, 3-(methylamino)propyl (meth)acrylamide,2-(ethylamino)ethyl (meth)acrylamide, 3-(ethylamino)propyl(meth)acrylamide, 2-(tert-butylamino)ethyl (meth)acrylamide, and3-(tert-butylamino)propyl (meth)acrylamide. Vinyl amine may alsorepresent a suitable co-monomer in some cases.

Alpha olefins are another type of ethylenically unsaturated monomer thatmay be present as a co-monomer in the polymer nanoparticles disclosedherein. Suitable alpha olefins that the may be present in the polymernanoparticles of the present disclosure include, but are not limited to,ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, orany combination thereof. Linear alpha olefins having an even number ofcarbon atoms may be particularly suitable due to their ready commercialavailability.

Still other examples of ethylenically unsaturated monomers that may bepresent in the polymer nanoparticles of the present disclosure include,for example, styrene or substituted variants thereof; vinyl esters, suchas vinyl acetate, vinyl alkanoates or their derivatives; nitriles suchas (meth)acrylonitrile and fumaronitrile; ethylenically unsaturatedhalides such as vinyl chloride and vinylidene chloride, any of which maybe present in combination with one or more of the ethylenicallyunsaturated monomers listed above.

Still other examples of ethylenically unsaturated monomers that may bepresent as a co-monomer in the polymer nanoparticles of the presentdisclosure include, but are not limited to, methyl vinyl ketone, ethylvinyl ketone, butyl vinyl ketone, acrolein, methacrolein,crotonaldehyde, acetoacetoxyethyl (meth)acrylate (AAEM), glycidyl(meth)acrylate, and any combination thereof.

Ethylenically unsaturated monomers bearing at least one acidic group mayalso be present as a co-monomer in the polymer nanoparticles of thepresent disclosure. Such ethylenically unsaturated monomers may bear aside chain carboxylic acid or sulfonic acid. Illustrative examples mayinclude, but are not limited to, maleic acid, methyl hydrogen maleate,ethyl hydrogen maleate, itaconic acid, fumaric acid, crotonic acid,citraconic acid, styrenesulfonic acid, and 2-aminomethylpropanesulfonicacid derivatized with a vinyl group. Carboxylic acid forms of theforegoing monomers may be present in an esterified form as well, such asmethyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl or likeesterified form. Other suitable esterified monomers may comprise anethylenically unsaturated group in the alcohol-derived portion of theesterified monomer. Such ethylenically unsaturated monomers may include,for example, vinyl acetate, allyl acetate, vinyl propionate, allylpropionate, vinyl benzoate, allyl benzoate, and the like.

Polymerization to afford a crosslinked fluorinated polymer utilizing anyof the foregoing fluorinated (meth)acrylic monomers, ethylenicallyunsaturated co-monomers, and crosslinkers may be conducted via emulsionpolymerization in non-limiting embodiments. Once polymerization hastaken place under suitable emulsion polymerization conditions to afforda crosslinked fluorinated polymer, polymer nanoparticles may be obtainedin at least partially isolated form by removing solvent from theemulsion (e.g., by spray drying or evaporation) and/or by removing thepolymer nanoparticles from the emulsion (e.g., by filtration orcentrifugation). Suitable emulsion polymerization conditions will befamiliar to one having ordinary skill in the art and are summarized inbrief hereinafter.

Suitable emulsion polymerization conditions may feature an aqueous fluidin which emulsion polymerization takes place. Aqueous fluids suitablefor use in the present disclosure may comprise water or water admixedwith a water-miscible organic solvent, such as an alcohol or a glycol.The aqueous fluids and the resulting polymer emulsions may be acidic,neutral, or basic, depending upon particular application needs. Aparticular pH may be chosen to maintain or break the emulsion, forexample, optionally with buffering, if needed. Suitable pH values duringemulsion polymerization may range from about 1 to about 7, or about 2 toabout 6, or about 1 to about 6, or about 6 to about 7, or about 6 toabout 8, or about 7 to about 8, or about 7 to about 14, or about 8 toabout 14, or about 8 to about 12, or about 7 to about 9.

The aqueous fluid may comprise at least one surfactant to promoteemulsification, according to some embodiments. Suitable surfactants maybe cationic, anionic, zwitterionic, non-ionic, or any combinationthereof. Illustrative non-ionic surfactants may include, for example,alkylaryl polyether alcohols, alkylphenol ethoxylates, alkylethoxylates, polyoxamers, fatty acid esters (e.g., fatty acid glycerolesters, fatty acid sorbitan esters, fatty acid sorbitol esters, fattyacid lecithin esters, and the like), polyethylene oxide sorbitan fattyacid esters, and any combination thereof. Polymer colloids such aspolyvinyl alcohol, polyvinylpyrrolidone, hydroxyethylcellulose and othercellulose derivatives, and the like may also comprise suitable non-ionicsurfactants. Illustrative anionic surfactants that may be suitable foruse in the disclosure herein include, but are not limited to, alkylethoxylate sulfates, alkyl ethoxylate sulfonates, alkylphenol ethoxylatesulfates, alkylphenol ethoxylate sulfonates, alkylsulfates,alkylsulfonates, alkylarylsulfates, alkylarylsulfonates,sulfosuccinates, and any combination thereof. Illustrative zwitterionicsurfactants that may be suitable for use in the disclosure hereininclude various betaines and sultaines. The at least one surfactant maybe present in the polymer emulsions of the present disclosure in anamount ranging from about 0.2 wt. % to about 10 wt. %, or about 0.2 wt.% to about 7 wt. % as measured against total solids.

Emulsion polymerization of ethylenically unsaturated monomers may takeplace in the presence of at least one radical initiator. The at leastone radical initiator may be present at about 0.1 to about 8 percent byweight of the monomers undergoing polymerization. Suitable radicalinitiators may be capable of promoting radical polymerization underthermal conditions or photolytic conditions when in the emulsion. Suchradical initiators may include, but are not limited to, sodiumpersulfate or other alkali metal persulfates, ammonium persulfate, azocompounds (e.g., 4,4′-azobis-cyanovaleric acid and/or AIBN), redoxsystems comprising sodium hydroxymethane sulfonate (sodium formaldehydesulfoxylate) and reducing agents such as ascorbic acid, oxidizinginitiators such as t-butyl-hydroperoxide, the like, and any combinationthereof. Other suitable radical initiators may include azoamidinecompounds such as, for example,2,2′-azobis(2-methyl-N-phenylpropionamidine) dihydrochloride,2,2′-azobis[N-(4-chlorophenyl)-2-methylpropionamidine]di-hydrochloride,2,2′-azobis[N-(4-hydroxyphenyl)-2-methylpropionamidine]dihydrochloride,2,2′-azobis[N-(4-amino-phenyl)-2-methylpropionamidine]tetrahydrochloride,2,2′-azobis[2-methyl-N(phenylmethyl)propionamidine]dihydrochloride,2,2′-azobis[2-methyl-N-2-propenylpropionamidine]dihydrochloride,2,2′-azobis[N-(2-hydroxy-ethyl)-2-methylpropionamidine]dihydrochloride,2,2′-azobis[2(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride,2,2′-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride,2,2′-azobis[2-(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl)propane]dihydrochloride,2,2′-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride,2,2′-azobis[2-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochloride,2,2′-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride,combinations thereof, and the like. Thermal radical polymerizationcondition may occur at a temperature ranging from about 20° C. to about90° C.

Once formed by emulsion polymerization, polymer nanoparticles may berecovered by any suitable technique such as filtration, centrifugation,spray drying, any combination thereof, and the like.

Additional nanoparticles may be present in combination with the polymernanoparticles upon the outer surface of the thermoplastic particulates,particularly inorganic nanoparticles selected from a plurality of oxidenanoparticles, carbon black, or any combination thereof. Oxidenanoparticles suitable for use in the present disclosure may include,for example, silica nanoparticles, titania nanoparticles, zirconiananoparticles, alumina nanoparticles, iron oxide nanoparticles, copperoxide nanoparticles, tin oxide nanoparticles, boron oxide nanoparticles,cerium oxide nanoparticles, thallium oxide nanoparticles, tungsten oxidenanoparticles, or any combination thereof. Mixed oxides formed asnanoparticles, such as aluminosilicates, borosilicates, andaluminoborosilicates, for example, are also encompassed by the term“oxide” and may be suitable for use in the disclosure herein. The oxidenanoparticles may be hydrophilic or hydrophobic in nature, which may benative to the nanoparticles or result from surface treatment of thenanoparticles. For example, silica nanoparticles having a hydrophobicsurface treatment, such as dimethylsilyl, trimethylsilyl, or the like,may be formed through reacting hydrophilic surface hydroxyl groups withan appropriate functionalizing agent. Hydrophobically functionalizedoxide nanoparticles may be particularly desirable in the methods andcompositions of the present disclosure, although unfunctionalized oxidenanoparticles or hydrophilically modified oxide nanoparticles may alsobe suitable for use as well. For example, hydrophobically functionalizedoxide nanoparticles may be particularly compatible with the hydrophobicfluids employed as carrier fluids in melt emulsification processes, asdiscussed further below.

Silica nanoparticles, particularly fumed silica nanoparticles with ahydrophobic functionalization thereon, may be especially suitable foruse in combination with polymer nanoparticles in the disclosure herein,since a wide variety of functionalized silicas are available withdifferent types of hydrophobic functionalizations and at a range ofparticle sizes. Silazane and silane hydrophobic functionalizations areamong the hydrophobic functionalizations that may be present in silicananoparticles compatible for use in the present disclosure. Thecombination of polymer nanoparticles and silica nanoparticles may conveyspecified properties to the thermoplastic particulates, or aconsolidated object formed therefrom, that may not be realized whenusing silica nanoparticles or polymer nanoparticles alone.

Hydrophobic functionalization may make silica nanoparticles lesscompatible with water than are unfunctionalized silica nanoparticles.Suitable hydrophobic functionalization may be non-covalently orcovalently attached to a surface of the silica nanoparticles. Covalentattachment may take place, for example, through functionalization ofsurface hydroxyl groups on the surface of the silica nanoparticles. In anon-limiting example, silica nanoparticles may be treated withhexamethyldisilazane to afford covalent attachment of a hydrophobicfunctionalization. Commercially available hydrophobically functionalizedsilica nanoparticles usable in combination with polymer nanoparticlesmay include, but are not limited to, Aerosil RX50 (Evonik, averageparticle size=40 nm) and Aerosil R812S (Evonik, average particle size=7nm).

Carbon black is another type of nanoparticle that may be present uponthermoplastic particulates in combination with polymer nanoparticles inthe disclosure herein. Various grades of carbon black will be familiarto one having ordinary skill in the art, any of which may be suitablefor use in the disclosure herein. Various types of oxide nanoparticlesmay also be present in combination with polymer nanoparticles in thedisclosure herein in some instances.

The loading and particle size of nanoparticles of various types upon thethermoplastic particulates of the present disclosure may vary over awide range. The nanoparticle loading upon the polymer nanoparticles orsimilar types of nanoparticles may depend upon the nanoparticleconcentration(s) in a carrier fluid used to promote thermoplasticparticulate formation under melt emulsification conditions, as describedfurther below. In non-limiting examples, the concentration ofnanoparticles in the carrier fluid may range from about 0.01 wt. % toabout 10 wt. %, or about 0.05 wt. % to about 10 wt. %, or about 0.05 wt.% to about 5 wt. %, or about 0.1 wt. % to about 2 wt. %, or about 0.25wt. % to about 1.5 wt. %, or about 0.2 wt. % to about 1.0 wt. %, orabout 0.25 wt. % to about 1 wt. %, or about 0.25 wt. % to about 0.5 wt.% with respect to the weight of the thermoplastic polymer. The foregoingweight percentages refer to the weight percentage of polymernanoparticles that may be present or a combined weight percentage ofpolymer nanoparticles and at least one other type of nanoparticle, suchas silica nanoparticles. When polymer nanoparticles are used incombination with another type of nanoparticle, the polymer nanoparticlesand the at least one other type of nanoparticle (e.g., silicananoparticles) may be present in combination with one another in anyratio ranging from about 1:99 to about 99:1 on a weight basis.

The particle size of the nanoparticles, particularly polymernanoparticles may range from about 1 nm to about 100 nm, althoughparticles sizes up to about 500 nm may also be acceptable. The foregoingmay represent D₅₀ values. In non-limiting examples, the particle size ofthe nanoparticles, particularly polymer nanoparticles, may range fromabout 5 nm to about 500 nm, or about 5 nm to about 100 nm, or about 5 nmto about 75 nm, or about 5 nm to about 50 nm, or about 5 nm to about 10nm, or about 10 nm to about 20 nm, or about 20 nm to about 30 nm, orabout 30 nm to about 40 nm, or about 40 nm to about 50 nm, or about 50nm to about 60 nm. When polymer nanoparticle are present in combinationwith another type of nanoparticle, such as silica nanoparticles, thesize of the polymer nanoparticles may be substantially the same as ordiffer from the size of the other type of nanoparticles, such as silicananoparticles. When used in combination, the polymer nanoparticles maybe larger or smaller than the other type of nanoparticles.

Silica nanoparticles and similar oxide nanoparticles suitable for use inthe disclosure herein in combination with polymer nanoparticles, mayhave a BET surface area of about 10 m²/g to about 500 m²/g, or about 10m²/g to about 150 m²/g, or about 25 m²/g to about 100 m²/g, or about 100m²/g to about 250 m²/g, or about 250 m²/g to about 500 m²/g.

Particular examples of oxide nanoparticles suitable for use in thedisclosure herein in combination with polymer nanoparticles may includethose treated with an alkyl silane, such as hexamethyldisilazane (HMDS),dimethyldichlorosilane, or other long-chain alkyl silanes such asdecyltriethoxysilane or octyltriethoxysilane, for example. Suitableoxide nanoparticles may vary from about 7 nm to about 130 nm in size.Specific commercial examples of hydrophobically treated silicas, theirparticle sizes, and their hydrophobic treatment may include thefollowing: Wacker HDK® H13TD (16 nm, PDMS), HDK® H13TM (16 nm, HMDS),HDK® H13TX (16 nm, HMDS/PDMS), HDK® H20TD (12 nm, PDMS), HDK® H20TM (12nm, HMDS), HDK® H20TX (12 nm, HMDS/PDMS), HDK® H30TD (8 nm, PDMS), HDK®H30TM (8 nm, HMDS), HDK® H30TX (8 nm, HMDS/PDMS), HDK® H3004 (12 nm,HMDS), HDK® HOSTD (40 nm, PDMS), HDK® HO5TM (40 nm, HMDS), HDK® HO5TX(40 nm, HMDS/PDMS); Evonik R972 (16 nm, DDS), RY200S (16 nm, PDMS, BETsurface area=200 m²/g), R202 (16 nm, PDMS), R974 (12 nm, DDS), RY200 (12nm, PDMS), RX200 (12 nm, HMDS), R8200 (12 nm, HMDS), R805 (12 nm, alkylsilane), R104 (12 nm, alkyl silane), RX300 (7 nm, HMDS), R812 (7 nm,HMDS), R812S (7 nm, HMDS, BET surface area=300 m²/g), R106 (7 nm, alkylsilane), NY50 (30 nm, PDMS), NAX50 (30 nm, HMDS), RY50 (40 nm, PDMS),and RX50 (40 nm, HMDS); Cabot TS530 (8 nm, HMDS); and Shin-Etsu sol-gelsilicas X24-9163A (110 nm, HMDS, BET surface area=25 m²/g) andX24-9600A-80 (80 nm, HMDS, BET=40 m²/g).

Suitable oxide nanoparticles may also include treatments including basesor base salts. Specific commercial examples of such treated oxidenanoparticles, their particle sizes, and their treatment include thefollowing types of silica nanoparticles: Wacker treated silicas HDK®H13TA (16 nm, PDMS −NR₂/NR₃ ⁺), HDK® H30TA (8 nm, PDMS −NR₂/NR₃ ⁺), HDK®H2015EP (12 nm, PDMS −NR₂/NR₃ ⁺), HDK® H2050EP (10 nm, PDMS −NR₂/NR₃ ⁺),HDK® H2150VP (10 nm, PDMS −NR₂/NR₃ ⁺), and HDK® H3050VP (8 nm, PDMS−NR₂/NR₃ ⁺).

Other suitable oxide nanoparticles, including both treated and untreatedvariants thereof, may include titanates. Suitable titanates may include,for example, CaTiO₃, BaTiO₃, MgTiO₃, MnTiO₃, SrTiO₃ and. Al₂TiO₅.

Also suitable for use in the disclosure herein in combination withpolymer nanoparticles are treated or untreated aluminum oxides. Specificcommercial examples of aluminum oxides, their particle sizes, and theirtreatment include, for instance, Evonik C805 (13 nm, octylsilane),Aluminum Oxide C (13 nm, untreated), Aeroxide Alu C 100 (10 nm,untreated), Aeroxide Alu C 130 (13 nm, untreated); Cabot SpectrAL 81 (21nm, untreated), and Cabot SpectrAl 100 (18 nm, untreated).

Still other suitable oxide nanoparticles suitable for use in combinationwith polymer nanoparticles may include treated or untreated titaniumdioxides. Examples of suitable commercial titanium dioxides may includeJMT-150IB from Tayca Corp., having a volume average particle diameter of15 nm, JMT2000 from Tayca Corp., having particle dimensions of 15×15×40nm, T805 from Evonik having a volume average particle diameter of about21 nm, SMT5103 from Tayca Corporation having a particle size of about 40nm, and STT-100H from Inabata America Corporation of average size ofabout 40 nm.

Based on turbidity measurements, about 80-90% of the availablenanoparticles, such as polymer nanoparticles or silica nanoparticles,may become associated with thermoplastic particulates formed throughmelt emulsification according to the disclosure herein. Since theloading of nanoparticles is measured relative to the thermoplasticpolymer, the amount of nanoparticles associated with the thermoplasticparticulates may be about 80-90% of the nanoparticle loading used whenforming the theremoplastic particulates. Higher or lower amounts ofnanoparticles may become associated with the thermoplastic particulateswhen higher or lower nanoparticle loadings are employed in the carrierfluid.

The thermoplastic particulates of the present disclosure may have thenanoparticles, particularly polymer nanoparticles, at least partiallyembedded in the outer surface of the thermoplastic particulates. Whenembedment occurs, a portion of the nanoparticle structure may be locatedin a crater or depression in the outer surface, thereby making it moredifficult to dislodge the nanoparticles from the surface. It is to beappreciated that even when substantial embedment does not occur,appropriately functionalized nanoparticles, such as hydrophobicallyfunctionalized silica nanoparticles or polymer nanoparticles, maynon-covalently associate (e.g., in a van der Waals-type interaction) topromote retention of the nanoparticles upon the outer surface.

Examples of thermoplastic polymers suitable for use in the disclosureherein include, but are not limited to, polyamides (e.g., Nylon-6,Nylon-12, and the like), polyurethanes, polyethylenes, polypropylenes,polyacetals, polycarbonates, polyethylene or polybutyleneterephthalates, glycol-modified polyethyelene terephthalates orpolybutylene terephthalates, polystyrenes, polyvinyl chlorides,polytetrafluoroethenes, polylactic acid and other polyesters,polyethers, polyether sulfones, polyetherether ketones, polyacrylates,polymethacrylates, polyimides, acrylonitrile butadiene styrene (ABS),polyphenylene sulfides, vinyl polymers, polyarylene ethers, polyarylenesulfides, polysulfones, polyether ketones, polyaryl ether ketones(PAEK), polyamide-imides, polyetherimides, polyetheresters, copolymerscomprising a polyether block and a polyamide block (PEBA or polyetherblock amide), grafted or ungrafted thermoplastic polyolefins,functionalized or nonfunctionalized ethylene/vinyl monomer polymers,functionalized or nonfunctionalized ethylene/alkyl (meth)acrylates,functionalized or nonfunctionalized (meth)acrylic acid polymers,functionalized or nonfunctionalized ethylene/vinyl monomer/alkyl(meth)acrylate terpolymers, ethylene/vinyl monomer/carbonyl terpolymers,ethylene/alkyl (meth)acrylate/carbonyl terpolymers,methylmethacrylate-butadiene-styrene (MBS)-type core-shell polymers,polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM)block terpolymers, chlorinated or chlorosulphonated polyethylenes,polyvinylidene fluoride (PVDF), phenolic resins, poly(ethylene/vinylacetate)s, polybutadienes, polyisoprenes, styrenic block copolymers,polyacrylonitriles, silicones, the like, and any combination thereof.Copolymers comprising one or more of the foregoing may also be used inthe present disclosure. Any of the foregoing polymers may bethermoplastic elastomers and comprise a crystalline “hard” segment andan amorphous “soft” segment.

Particularly suitable examples of thermoplastic polymers for use in thedisclosure herein may include polyamides, such as Nylon-6 or Nylon-12;acrylonitrile butadiene styrene; polylactic acid; polyurethanes;poly(arylene ether)s; polyaryletherketones; polycarbonates; polyimides;polyphenylene sulfides; poly(arylene sulfone)s; polyesters, such aspolyethylene terephthalate or polybutylene terephthalate orglycol-modified variants thereof; and any combination thereof.

More specific examples of suitable polyamides may include, but are notlimited to, polycaproamide (Nylon 6, polyamide 6, or PA6),poly(hexamethylene succinamide) (Nylon 46, polyamide 46, or PA46),polyhexamethylene adipamide (Nylon 66, polyamide 66, or PA66),polypentamethylene adipamide (Nylon 56, polyamide 56, or PA56),polyhexamethylene sebacamide (Nylon 610, polyamide 610, or PA610),polyundecaamide (Nylon 11, polyamide 11, or PA11), polydodecaamide(Nylon 12, polyamide 12, or PA12), and polyhexamethylene terephthalamide(Nylon 6T, polyamide 6T, or PA6T), Nylon 10.10 (polyamide 10.10 orPA10.10), Nylon 10.12 (polyamide 10.12 or PA10.12), Nylon 10.14(polyamide 10.14 or PA10.14), Nylon 10.18 (polyamide 10.18 or PA10.18),Nylon 6.10 (polyamide 6.10 or PA6.10), Nylon 6.18 (polyamide 6.18 orPA6.18), Nylon 6.12 (polyamide 6.12 or PA6.12), Nylon 6.14 (polyamide6.14 or PA6.14), semi-aromatic polyamide, the like, and any combinationthereof. Copolyamides may also be used. Examples of suitablecopolyamides include, but are not limited to, PA 11/10.10, PA 6/11, PA6.6/6, PA 11/12, PA 10.10/10.12, PA 10.10/10.14, PA 11/10.36, PA11/6.36, PA 10.10/10.36, and the like, and any combination thereof.Polyesteramides, polyetheresteramides, polycarbonate-esteramides, andpolyether-block-amides, any which may be elastomeric, may also be usedin the disclosure herein.

Examples of suitable polyurethanes include, but are not limited to,polyether polyurethanes, polyester polyurethanes, mixed polyether andpolyester polyurethanes, the like, and any combination thereof. Suitablepolyurethanes may include elastomeric polyurethanes, which are preparedby condensation of an isocyanate, a polyol, and a chain extender, wherethe polyols impart flexibility to the polymer chain and typicallyconstitute a soft segment. Examples of suitable polyurethanes for use inthe present disclosure include, but are not limited to,poly[4,4′-methylenebis(phenylisocyanate)-alt-1,4-butanediol/di(propyleneglycol)/polycaprolactone],ELASTOLLAN® 1190A (a polyether polyurethane elastomer, available fromBASF), the like, and any combination thereof.

Suitable polyesters are a condensation reaction product formed from adiacid and a diol, or a self-condensation reaction product of ahydroxyacid, such as lactic acid. Glycol-modified polyesters, such asglycol-modified polyethylene terephthalate or glycol-modifiedpolybutylene terephthalate may be particularly suitable for use in thedisclosure herein. Glycol modification may impart desirable benefitssuch as optical transparency and flexibility of the polymer chain.

Suitable thermoplastic polymers may be elastomeric or non-elastomeric.Some of the foregoing examples of thermoplastic polymers may beelastomeric or non-elastomeric depending on the specific composition ofthe polymer. For example, polyethylene that is a copolymer of ethyleneand propylene may be elastomeric or not depending on the amount ofpropylene present in the polymer.

Elastomeric thermoplastic polymers suitable for use in the disclosureherein generally fall within one of six classes: styrenic blockcopolymers, thermoplastic polyolefin elastomers, thermoplasticvulcanizates (also referred to as elastomeric alloys), thermoplasticpolyurethanes, thermoplastic copolyesters, and thermoplastic polyamides(typically block copolymers comprising polyamide). Particular examplesof elastomeric thermoplastic polymers can be found in Handbook ofThermoplastic Elastomers, 2nd ed., B. M. Walker and C. P. Rader, eds.,Van Nostrand Reinhold, New York, 1988. Examples of suitable elastomericthermoplastic polymers include, but are not limited to, elastomericpolyamides, polyurethanes, copolymers comprising a polyether block and apolyamide block (PEBA or polyether block amide), methylmethacrylate-butadiene-styrene (MBS)-type core-shell polymers,polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM)block terpolymers, polybutadienes, polyisoprenes, styrenic blockcopolymers, and polyacrylonitriles), silicones, and the like.Elastomeric styrenic block copolymers may include at least one blockselected from the group of isoprene, isobutylene, butylene,ethylene/butylene, ethylene-propylene, and ethylene-ethylene/propylene.More specific elastomeric styrenic block copolymer examples include, butare not limited to, poly(styrene-ethylene/butylene),poly(styrene-ethylene/butylene-styrene),poly(styrene-ethylene/propylene), styrene-ethylene/propylene-styrene),poly(styrene-ethylene/propylene-styrene-ethylene-propylene),poly(styrene-butadiene-styrene),poly(styrene-butylene-butadiene-styrene), and the like, and anycombination thereof.

FIG. 1 is a flow chart of non-limiting example method 100 for producingthermoplastic particulates in accordance with the present disclosure. Asshown, thermoplastic polymer 105, carrier fluid 104, and polymernanoparticles 106 are combined 108 to produce mixture 110. Optionally,other nanoparticles, such as silica nanoparticles, may be present incombination with polymer nanoparticles 106. Thermoplastic polymer 105,carrier fluid 104, and nanoparticles 106 may be combined 108 in anyorder, with mixing and/or heating being conducted. In a particularexample, carrier fluid 104 may be heated above a melting point orsoftening temperature of thermoplastic polymer 105 before combining theother components therewith. Alternately, all the components may be mixedtogether in carrier fluid 104 and then heated above the melting point orsoftening temperature. Polymer nanoparticles 106 may remain as a solidat the heating temperature so that they can become disposed upon theouter surface of the resulting thermoplastic particulates following meltemulsification.

Heating above the melting point or softening temperature ofthermoplastic polymer 105 may be at any temperature below thedecomposition temperature or boiling point of any of the components inthe melt emulsion. In non-limiting examples, heating at a temperatureabout 1° C. to about 50° C., or about 1° C. to about 25° C., or about 5°C. to about 30° C., or about 20° C. to about 50° C. above the meltingpoint or softening temperature of thermoplastic polymer 105 may beconducted. In the disclosure herein, melting points may be determined byASTM E794-06(2018) with 10° C./min ramping and cooling rates. Thesoftening temperature or softening point of a thermoplastic polymer,unless otherwise specified, may be determined by ASTM D6090-17. Thesoftening temperature can be measured by using a cup and ball apparatusavailable from Mettler-Toledo using a 0.50 gram sample with a heatingrate of 1° C./min. Melting points or softening temperatures ofthermoplastic polymer 105 in the present disclosure may range from about50° C. to about 400° C. In more particular examples, the heatingtemperature may range from about 100° C. to about 300° C. or about 200°C. to about 250° C., provided that thermoplastic polymer 105 melts orsoftens within this range.

Mixture 110 is then processed 112 by applying sufficient shear toproduce liquefied droplets of thermoplastic polymer 105 at a temperaturegreater than the melting point or softening temperature of thermoplasticpolymer 105, thereby forming melt emulsion 114. Without being limited bytheory, it is believed that, all other factors being the same,increasing shear may decrease the size of the liquefied droplets incarrier fluid 104. It is to be understood that at some point there maybe diminishing returns on increasing shear and decreasing the dropletsize in turn and/or disruptions to the droplet contents at higher shearrates. Examples of mixing apparatuses suitable for producing meltemulsion 114 include, but are not limited to, extruders (e.g.,continuous extruders, batch extruders and the like), stirred reactors,blenders, reactors with inline homogenizer systems, and the like, andapparatuses derived therefrom.

In non-limiting examples, the liquefied droplets may have a size ofabout 1 μm to about 1,000 μm, or about 1 μm to about 500 μm, or about 25μm to about 500 μm, or about 1 μm to about 200 μm, or about 1 μm toabout 150 μm, or about 1 μm to about 130 μm, or about 1 μm to about 100μm, or about 10 μm to about 150 μm, or about 10 μm to about 100 μm, orabout 20 μm to about 80 μm, or about 20 μm to about 50 μm, or about 50μm to about 90 μm. The resulting thermoplastic particulates formed aftersolidification may reside within similar size ranges. That is, thethermoplastic particulates in the particulate compositions and methodsof the present disclosure may have a size of about 1 μm to about 1,000μm, or about 1 μm to about 500 μm, or about 25 μm to about 500 μm, orabout 1 μm to about 200 μm, or about 1 μm to about 150 μm, or about 1 μmto about 130 μm, or about 1 μm to about 100 μm, or about 1 μm to about200 μm, or about 10 μm to about 100 μm, or about 20 μm to about 80 μm,or about 20 μm to about 50 μm, or about 50 μm to about 90 μm. Particlesize measurements may be made by analysis of optical images or usingonboard software of a Malvern Mastersizer 3000 Aero S instrument, whichuses light scattering techniques for particle size measurement.

For light scattering techniques, glass bead control samples with adiameter within the range of 15 μm to 150 μm under the tradename QualityAudit Standards QAS4002™ obtained from Malvern Analytical Ltd. may beused. Samples may be analyzed as dry powders dispersed in air using thedry powder dispersion module of the Mastersizer 3000 Aero S. Particlesizes may be derived using the instrument software from a plot of volumedensity as a function of size.

Melt emulsion 114 is then cooled 116 to solidify the liquefied dropletsinto thermoplastic particulates in a solidified state. The cooling ratemay range from about 100° C./sec to about 10° C./hour or about 10°C./sec to about 10° C./hr, including any cooling rate in between. Shearmay be discontinued during cooling, or may be maintained at the samerate or a different rate during cooling. Cooled mixture 118 can then betreated 120 to isolate thermoplastic particulates 122 from othercomponents 124 (e.g., carrier fluid 104, excess polymer nanoparticles106, and the like). Washing, filtering and/or the like may be conductedat this stage to purify thermoplastic particulates 122 further, whereinthermoplastic particulates 122 comprise thermoplastic polymer 105, andat least a portion of polymer nanoparticles 106 coating the outersurface of thermoplastic particulates 122. Depending upon non-limitingfactors such as the temperature (including cooling rate), the type ofthermoplastic polymer 105, and the types and sizes of polymernanoparticles 106, polymer nanoparticles 106 may become at leastpartially embedded within the outer surface of thermoplasticparticulates 122 in the course of becoming disposed thereon. Evenwithout embedment taking place, polymer nanoparticles 106 may remainrobustly associated with thermoplastic particulates 122 to facilitatetheir further use.

In the foregoing, thermoplastic polymer 105 and carrier fluid 104 arechosen such that these components are immiscible or substantiallyimmiscible (<1 wt. % solubility) at the various processing temperatures(e.g., from room temperature to the temperature at which liquefieddroplets are formed and maintained as two or more phases).

After separating thermoplastic particulates 122 from other components124, further processing 126 of thermoplastic particulates 122 may takeplace. In a non-limiting example further processing 126 may include, forexample, sieving thermoplastic particulates 122 and/or blendingthermoplastic particulates 122 with other substances to form processedthermoplastic particulates 128. Processed thermoplastic particulates 128may be formulated for use in a desired application, such as additivemanufacturing in a non-limiting example.

The thermoplastic particulates may have a bulk density of about 0.3g/cm³ to about 0.8 g/cm³, or about 0.3 g/cm³ to about 0.6 g/cm³, orabout 0.4 g/cm³ to about 0.7 g/cm³, or about 0.5 g/cm³ to about 0.6g/cm³, or about 0.5 g/cm³ to about 0.8 g/cm³.

Shear sufficient to form liquefied droplets may be applied throughstirring the carrier fluid in particular examples of the presentdisclosure. In non-limiting examples, the stirring rate may range fromabout 50 rotations per minute (RPM) to about 1500 RPM, or about 250 RPMto about 1000 RPM, or about 225 RPM to about 500 RPM, or about 1000 RPMto about 2000 RPM. The stirring rate while melting the thermoplasticpolymer may be the same as or different than the stirring rate used onceliquefied droplets have formed. The liquefied droplets may be stirredover a stirring time of about 30 seconds to about 18 hours or longer, orabout 1 minute to about 180 minutes, or about 1 minute to about 60minutes, or about 5 minutes to about 6 minutes, or about 5 minutes toabout 30 minutes, or about 10 minutes to about 30 minutes, or about 30minutes to about 60 minutes.

Loading (concentration) of the thermoplastic polymer in the carrierfluid may vary over a wide range. In non-limiting examples, the loadingof the thermoplastic polymer in the carrier fluid may range from about 1wt. % to about 99 wt. % relative to the weight of the carrier fluid. Inmore particular examples, the loading of the thermoplastic polymer mayrange from about 5 wt. % to about 75 wt. %, or about 10 wt. % to about60 wt. %, or about 20 wt. % to about 50 wt. %, or about 20 wt. % toabout 30 wt. %, or about 30 wt. % to about 40 wt. %, or about 40 wt. %to about 50 wt. %, or about 50 wt. % to about 60 wt. % relative to theweight of the carrier fluid. The thermoplastic polymer may be present inan amount ranging from about 5 wt. % to about 60 wt. %, or about 5 wt. %to about 25 wt. %, or about 10 wt. % to about 30 wt. %, or about 20 wt.% to about 45 wt. %, or about 25 wt. % to about 50 wt. %, or about 40wt. % to about 60 wt. % relative to a combined amount of thethermoplastic polymer and the carrier fluid.

Upon forming thermoplastic particulates in the presence of nanoparticlesaccording to the disclosure herein, at least a portion of the polymernanoparticles and/or other types of nanoparticles may be disposed as acoating or partial coating upon the outer surface of the thermoplasticparticulates. The coating may be disposed substantially uniformly uponthe outer surface in some cases. As used herein with respect to acoating, the term “substantially uniform” refers to an even coatingthickness in surface locations covered by the nanoparticles,particularly the entirety of the outer surface. Coating coverage uponthe thermoplastic particulates may range from about 5% to about 100%, orabout 5% to about 25%, or about 20% to about 50%, or about 40% to about70%, or about 50% to about 80%, or about 60% to about 90%, or about 70%to about 100% of the surface area of the particulates. Coverage may bedetermined by image analysis of SEM micrographs.

Carrier fluids suitable for use in the disclosure herein include thosein which the thermoplastic polymer and polymer nanoparticles aresubstantially immiscible with the carrier fluid, the carrier fluid has aboiling point exceeding the melting point or softening temperature ofthe thermoplastic polymer, and the carrier fluid has sufficientviscosity to form liquefied droplets of substantially spherical shapeonce the thermoplastic polymer has undergone melting or softeningtherein. Suitable carrier fluids may include, for example, silicone oil,fluorinated silicone oils, perfluorinated silicone oils, polyethyleneglycols, paraffins, liquid petroleum jelly, vison oils, turtle oils,soya bean oils, perhydrosqualene, sweet almond oils, calophyllum oils,palm oils, parleam oils, grapeseed oils, sesame oils, maize oils,rapeseed oils, sunflower oils, cottonseed oils, apricot oils, castoroils, avocado oils, jojoba oils, olive oils, cereal germ oils, esters oflanolic acid, esters of oleic acid, esters of lauric acid, esters ofstearic acid, fatty esters, higher fatty acids, fatty alcohols,polysiloxanes modified with fatty acids, polysiloxanes modified withfatty alcohols, polysiloxanes modified with polyoxy alkylenes, the like,and any combination thereof.

Suitable carrier fluids may have a density of about 0.6 g/cm³ to about1.5 g/cm³, and the thermoplastic polymer may have a density of about 0.7g/cm³ to about 1.7 g/cm³, wherein the thermoplastic polymer has adensity similar to, lower than, or higher than the density of thecarrier fluid. Blends of carrier fluids having differing viscositiesand/or density may be utilized to achieve an intermediate propertybetween that of the blend components.

Particularly suitable silicone oils include polysiloxanes. Illustrativesilicone oils suitable for use in the disclosure herein include, forexample, polydimethylsiloxane (PDMS), methylphenylpolysiloxane, an alkylmodified polydimethylsiloxane, an alkyl modifiedmethylphenylpolysiloxane, an amino modified polydimethylsiloxane, anamino modified methylphenylpolysiloxane, a fluorine modifiedpolydimethylsiloxane, a fluorine modified methylphenylpolysiloxane, apolyether modified polydimethylsiloxane, a polyether modifiedmethylphenylpolysiloxane, the like and any combination thereof.

In non-limiting examples, the carrier fluid and the thermoplasticpolymer may be heated at a temperature of about 200° C. or above.Suitable heating temperatures may be chosen based upon the melting pointor softening temperature of the thermoplastic polymer, the boiling pointof the carrier fluid, and a decomposition temperature of the polymernanoparticles. The cooling rate following formation of liquefied polymerdroplets may be varied as desired. In some instances, cooling may takeplace with heat dissipation to the surrounding environment taking placeat an innate (uncontrolled) rate once heating is discontinued. In othercases, cooling at a controlled rate (e.g., by gradually decreasing theheating temperature and/or using jacketed temperature control toincrease or decrease the rate of cooling may be employed.

Suitable carrier fluids, such as polysiloxanes, including PDMS, may havea viscosity at 25° C. of about 1,000 cSt to about 150,000 cSt, or about1,000 cSt to about 60,000 cSt, or about 40,000 cSt to about 100,000 cSt,or about 75,000 cSt to about 150,000 cSt. The viscosity of the carrierfluid may be obtained from commercial suppliers or it may be measured,if desired, through techniques known to persons having ordinary skill inthe art.

Separating the thermoplastic particulates from the carrier fluid maytake place by any of a variety of known separation techniques. Any ofgravity settling and filtration, decantation, centrifugation, or thelike may be used to separate the thermoplastic particulates from thecarrier fluid. The thermoplastic particulates may then be washed with asolvent in which the carrier fluid is soluble and the thermoplasticparticulates are insoluble in the course of the separation process. Inaddition, a solvent in which the carrier fluid is soluble and thethermoplastic particulates are insoluble may be mixed with the carrierfluid and the thermoplastic particulates before initially separating thethermoplastic particulates from the carrier fluid.

Suitable solvents for washing the thermoplastic particulates or mixingwith the carrier fluid may include, but are not limited to, aromatichydrocarbons (e.g., toluene and/or xylene), aliphatic hydrocarbons(e.g., heptane, n-hexane, and/or n-octane), cyclic hydrocarbons (e.g.,cyclopentane, cyclohexane, and/or cyclooctane), ethers (e.g. diethylether, tetrahydrofuran, diisopropyl ether, and/or dioxane), halogenatedhydrocarbons (e.g., dichloroethane, trichloroethane, dichloromethane,chloroform and/or carbon tetrachloride), alcohols (e.g., methanol,ethanol, isopropanol, and/or n-propanol), ketones (e.g., methyl ethylketone and/or acetone); esters (e.g., ethyl acetate and the like),water, the like, and any combination thereof. After washing thethermoplastic particulates, any of heating, vacuum drying, air drying,or any combination thereof may be performed.

At least a majority of the thermoplastic particulates obtained accordingto the disclosure here may be substantially spherical in shape. Moretypically, about 90% or greater, or about 95% or greater, or about 99%or greater of the thermoplastic particulates produced by meltemulsification according to the present disclosure may be substantiallyspherical in shape. In other non-limiting examples, the thermoplasticparticulates of the present disclosure may have a sphericity(circularity) of about 0.9 or greater, including about 0.90 to about1.0, or about 0.93 to about 0.99, or about 0.95 to about 0.99, or about0.97 to about 0.99, or about 0.98 to 1.0. Sphericity (circularity) maybe measured using a Sysmex FPIA-2100 Flow Particle Image Analyzer. Todetermine circularity, optical microscopy images are taken of theparticulates. The perimeter (P) and area (A) of the particulates in theplane of the microscopy image is calculated (e.g., using a SYSMEX FPIA3000 particle shape and particle size analyzer, available from MalvernInstruments). The circularity of the particulate is C_(EA)/P, whereC_(EA) is the circumference of a circle having the area equivalent tothe area (A) of the actual particulate.

The thermoplastic particulates of the present disclosure may have anangle of repose of about 25° to about 45°, or about 25° to about 35°, orabout 30° to about 40°, or about 35° to about 45°. Angle of repose maybe determined using a Hosokawa Micron Powder Characteristics Tester PT-Rusing ASTM D6393-14 “Standard Test Method for Bulk SolidsCharacterization by Carr Indices.”

Thermoplastic particulates isolated from the carrier fluid according tothe disclosure above may be further processed to make the thermoplasticparticulates suitable for an intended application. In one example, thethermoplastic particulates may be passed through a sieve or similarstructure having an effective screening size that is greater than theaverage particle size of the thermoplastic particulates. For example, anillustrative screening size for processing thermoplastic particulatessuitable for use in three-dimensional printing may have an effectivescreening size of about 150 μm. When referring to sieving, pore/screensizes are described per U.S.A. Standard Sieve (ASTM E11-17). Otherscreening sizes, either larger or smaller, may be more suitable forthermoplastic particulates destined for use in other applications.Sieving may remove larger particulates that may have formed during themelt emulsification process and/or remove agglomerated particulates thatmay have poor flow characteristics. In general, sieves having aneffective screening size ranging from about 10 μm to about 250 μm may beused.

In addition, the thermoplastic particulates, including sievedthermoplastic particulates, may be mixed with one or more additionalcomponents such as flow aids, fillers or other substances intended totailor the properties of the thermoplastic particulates for an intendedapplication. Mixing of the additional components with the thermoplasticparticulates may be conducted by dry blending techniques. Suitableexamples of flow aids (e.g., carbon black, graphite, silica, and thelike) and similar substances will be familiar to one having ordinaryskill in the art. Such flow aids differ from the nanoparticles includedin melt emulsification, since the flow aids are not robustly adhered tothe surface of the thermoplastic particulates when dry blending isperformed.

In particular applications, the particulate compositions disclosedherein may be utilized in additive manufacturing processes, especiallythose employing selective laser sintering or other powder bed fusionprocesses to promote particulate consolidation. Additive manufacturingmethods of the present disclosure may comprise providing a particulatecomposition of the present disclosure (a particulate compositioncomprising a plurality of thermoplastic particulates comprising athermoplastic polymer, and polymer nanoparticles disposed on an outersurface of the thermoplastic particulates), depositing the particulatecomposition layer-by-layer in a powder bed, and heating a portion of thepowder bed to consolidate a portion of the thermoplastic particulatesinto a consolidated part having a specified shape. The nanoparticles mayremain associated with the consolidated part once powder bed fusion hastaken place. Specifically, the consolidated part may comprise athermoplastic matrix formed by consolidation of thermoplasticparticulates, and at least polymer nanoparticles admixed with thethermoplastic matrix.

In particular process configurations, consolidation of the thermoplasticparticulates may take place using selective laser sintering. Suitableconditions for performing selective laser sintering or other powder bedparticulate consolidation processes to form a consolidated part are notbelieved to be especially limited. Lasers suitable for performingselective laser sintering may include both continuous wave lasers andpulsed wave lasers to provide the energy needed to promote consolidationof the thermoplastic particulates into a consolidated part. CO₂ lasersare commonly used to promote consolidation of thermoplastic particulatesduring additive manufacturing due to the high absorptivity of thepolymers to the CO₂ laser emission wavelength. The operating conditionsof the CO₂ laser or similar laser chosen to promote particulateconsolidation may be chosen such that particulate consolidation occursto a desired degree. Standard laser settings for promoting particulateconsolidation (e.g., power, scanning rate, bed temperature, and thelike) may be selected based on the knowledge of one having ordinaryskill in the art. The choice of particular conditions for conductingselective laser sintering or similar particulate consolidationtechniques may be influenced by non-limiting factors such as, forexample, the type of thermoplastic polymer being used, the size andcomposition of the thermoplastic particulates, the type of printedobject being produced, and the intended use conditions for the printedobject. Choice of the sintering conditions may, in non-limitingexamples, impact the porosity obtained following particulateconsolidation. Preferably, the thermoplastic matrix resulting fromparticulate consolidation may have a porosity of about 10% or below, orabout 5% or below, or about 2% or below, or about 1% or below.

Examples of printed objects formable using the particulate compositionsdisclosed herein are not considered to be particularly limited and mayinclude, for example, containers (e.g., for food, beverages, cosmetics,personal care compositions, medicine, and the like), shoe soles, toys,furniture parts, decorative home goods, plastic gears, screws, nuts,bolts, cable ties, medical items, prosthetics, orthopedic implants,production of artifacts that aid learning in education, 3D anatomymodels to aid in surgeries, robotics, biomedical devices (orthotics),home appliances, dentistry, automotive and airplane/aerospace parts,electronics, sporting goods, and the like.

Embodiments disclosed herein include:

A. Compositions comprising powder particulates. The particulatecompositions comprise: a plurality of thermoplastic particulatescomprising a thermoplastic polymer, and a plurality of polymernanoparticles disposed upon an outer surface of the thermoplasticparticulates, the polymer nanoparticles comprising a crosslinkedfluorinated polymer.

B. Methods for forming a printed object by particulate consolidation.The methods comprise: providing the particulate composition of A;depositing the particulate composition layer-by-layer in a powder bed;and heating a portion of the powder bed to consolidate a portion of thethermoplastic particulates into a consolidated part having a specifiedshape.

C. Consolidated parts prepared by the method of B. The consolidatedparts comprise a thermoplastic matrix formed by consolidation ofthermoplastic particulates; and polymer nanoparticles admixed with thethermoplastic matrix. D. Methods for forming powder particulates. Themethods comprise: combining a thermoplastic polymer and polymernanoparticles with a carrier fluid at a heating temperature at or abovea melting point or softening temperature of the thermoplastic polymerand below a melting point, softening temperature or decompositiontemperature of the polymer nanoparticles; wherein the thermoplasticpolymer and the polymer nanoparticles are substantially immiscible inthe carrier fluid at the heating temperature, and the polymernanoparticles comprise a crosslinked fluorinated polymer; applyingsufficient shear to disperse the thermoplastic polymer as liquefieddroplets in the carrier fluid at the heating temperature in the presenceof the polymer nanoparticles; after liquefied droplets have formed,cooling the carrier fluid to at least a temperature at whichthermoplastic particulates in a solidified state form, the thermoplasticparticulates comprising the thermoplastic polymer and at least a portionof the polymer nanoparticles disposed upon an outer surface of thethermoplastic particulates; and separating the thermoplasticparticulates from the carrier fluid.

Each of embodiments A, B, C and D may have one or more of the followingadditional elements in any combination:

Element 1: wherein the crosslinked fluorinated polymer comprises afluorinated (meth)acrylic monomer and a divinyl crosslinker.

Element 2: wherein the fluorinated (meth)acrylic monomer comprises2,2,2-trifluoroethyl (meth)acrylate and the divinyl crosslinkercomprises a divinylbenzene.

Element 3: wherein the crosslinked fluorinated polymer further comprisesan ethylenically unsaturated co-monomer differing from the fluorinated(meth)acrylic monomer.

Element 4: wherein the particulate composition further comprisesinorganic nanoparticles disposed upon the outer surface of thethermoplastic particulates, the inorganic nanoparticles comprising aplurality of oxide nanoparticles, carbon black, or any combinationthereof.

Element 5: wherein the oxide nanoparticles comprise silicananoparticles.

Element 6: wherein the thermoplastic particulates comprise about 0.01wt. % to about 10 wt. % polymer nanoparticles, as measured relative tothe thermoplastic polymer.

Element 7: wherein the thermoplastic particulates are substantiallyspherical and have a D₅₀ ranging from about 1 μm to about 1,000 μm.

Element 8: wherein the polymer nanoparticles range from about 5 nm toabout 500 nm in size.

Element 9: wherein heating takes place by selective laser sintering.

Element 10: wherein the polymer nanoparticles remain associated with theconsolidated part.

Element 11: wherein the polymer nanoparticles are obtained via emulsionpolymerization.

Element 12: wherein the method further comprises combining inorganicnanoparticles with the carrier fluid, the inorganic nanoparticlescomprising a plurality of oxide nanoparticles, carbon black, or anycombination thereof; wherein at least a portion of the inorganicnanoparticles are disposed upon the outer surface of the thermoplasticparticulates. Element 13: wherein the carrier fluid comprises a siliconeoil.

By way of non-limiting example, exemplary combinations applicable to A,B, C and D include, but are not limited to: 1 and 3; 1-3; 1 and 4; 1, 4and 5; 1 and 6; 1 and 7; 1 and 8; 4 and 5; 4 and 6; 4 and 7; 4 and 8; 6and 7; 6 and 8; and 7 and 8.

To facilitate a better understanding of the present disclosure, thefollowing examples of preferred or representative embodiments are given.In no way should the following examples be read to limit, or to define,the scope of the invention.

Examples

In the examples below, powder flow of thermoplastic particulates wascharacterized through sieving and angle of repose measurements. Sievingwas conducted using a 150 μm U.S.A. Standard Sieve (ASTM E11) withoutparticular conditions or duration of force. Angle of repose measurementswere performed using a Hosokawa Micron Powder Characteristics TesterPT-R using ASTM D6393-14 “Standard Test Method for Bulk SolidsCharacterization by Carr Indices.”

Average particle size measurements and particle size distributions forthe thermoplastic particulates were determined by light scattering usinga Malvern Mastersizer 3000 Aero S particle size analyzer. For such lightscattering techniques, glass bead control samples having a diameterwithin the range of 15 μm to 150 μm under the tradename Quality AuditStandards QAS4002™ obtained from Malvern Analytical Ltd. may be used.Samples may be analyzed as dry powders dispersed in air using the drypowder dispersion module of the Mastersizer 3000 Aero S instrument.Particle sizes may be derived using the instrument software from a plotof volume density as a function of size.

Average particle size measurements of polymer nanoparticles weredetermined by dynamic light scattering using a Nanotrac 252 instrument(MicroTrac, Inc.). This instrument uses a laser light-scatteringtechnique, Doppler-shifted light generated from each particle in motion(Brownian motion) is measured. The signals generated by these shifts areproportional to the size of the particles. The signals aremathematically converted to particle size and size distribution by theinstrument software. The analysis can be performed using an externalprobe or by inserting the probe into a fixed sample chamber. For suchlight scattering techniques, NIST polystyrene Nanosphere control sampleswith a diameter within the range of 15 nm to 150 nm under the tradenameNIST Traceable Reference Material for Nanotrac Particle Size Analyzersobtained from Microtrac may be used.

In the examples below, weight percentages are measured relative to thethermoplastic polymer unless otherwise specified.

Formation of Polymer Nanoparticles via Emulsion Polymerization. In a 2 LBuchi reactor, 6.5 g of CALFOAM® SLS-30 surfactant (sodium laurylsulfate at 30% solids, Pilot Chemical) was added to 816 g of deionizedwater. The reactor was deoxygenated by passing a stream of nitrogenthrough the reaction mixture and then ramped to 77° C. In a separate 1 Lglass vessel, a monomer emulsion was prepared by mixing together 223.6 gof trifluoroethyl methacrylate (TFEMA), 95.8 g of divinylbenzene (DVB),6.5 g CALFOAM® SLS-30 surfactant (at 30% solids) and 416 g deionizedwater. A 37.1 g seed amount was taken from the monomer emulsion andpumped into the 2 L reactor at 77° C. An initiator solution preparedfrom 1.22 g of ammonium persulfate in 34.3 g of deionized water was thenadded over 20 minutes to the reactor containing the seed emulsion. Theremaining monomer emulsion was then fed into the reactor over 120minutes. The stirring rate was increased after half of the monomeremulsion had been added. After all of the monomer emulsion had beenadded, the reaction mixture was maintained for 1 hour at 77° C.,followed by a 2 hour ramp to 87° C. and a 1 hour hold at thistemperature to reduce residual monomer following emulsionpolymerization. The resultant latex emulsion contained 20% percentsolids with an average particle size of 95 nm (spread: 8 nm to 6.54 μm)and melting point by TGA of 290.6° C. The latex was spray-dried toisolate the fluorinated polymer nanoparticles for subsequent meltemulsification.

Example 1: Polyurethane Particulates Coated with 1.0 Wt. % FluorinatedPolymer Nanoparticles. A 2 L Buchi reactor was loaded with PDMS oilhaving a viscosity of 30,000 cSt and pre-mixed with 1.0 wt. % of thefluorinated polymer nanoparticles prepared as above. Polyurethanepellets (ELASTOLAN 1190A10, BASF) were then added at 40 wt. % relativeto the PDMS oil. The reactor was stirred at 200 rpm under N₂ purge for10 minutes and then heated to 240° C. at a rate of 3.6° C./min. Thestirring rate was increased to 500 rpm when the temperature reachedaround 225° C. The melt dispersion was mixed at 500 rpm for anadditional 30 minutes with the N₂ shut off after the temperature reached235° C. After particulate formation had occurred, the hot slurry wasdischarged to a tray and cooled to room temperature. The resultantpolyurethane particulates were re-slurred 4 times in heptane andfiltered onto Whatman #1 90 mm filter paper to remove the PDMS oil. Thepolyurethane particulates had a D₅₀ of 81.8 microns (span=1.13) afterdrying to remove solvent. The angle of repose was 29.8°. FIG. 2 is ascanning electron microscope image of the polyurethane particulatesprepared in accordance with Example 1. FIG. 3 is a graph showing theparticle size distribution of the polyurethane particulates prepared inaccordance with Example 1.

For SLS printing, the particulates were further screened through a 250μm sieve. The particulates were then printed using a Snow White printerat 108° C. and 70% laser power.

Example 2: Polyurethane Particulates Coated with 1.5 Wt. % FluorinatedPolymer Nanoparticles. Example 1 was repeated except, 1.5 wt. % offluorinated polymer nanoparticles were used during melt emulsification.The resultant polyurethane particulates had a D₅₀ of 42.7 microns(span=0.89) after drying to remove solvent and screening through a 150μm sieve. The angle of repose was 31.0°.

Example 3: Polyurethane Particulates Coated with 0.75 Wt. % FluorinatedPolymer Nanoparticles. Example 1 was repeated except, 0.75 wt. % offluorinated polymer nanoparticles were used during melt emulsification.The resultant polyurethane particulates had a D₅₀ of about 81.5 microns(span=0.79) after drying to remove solvent and screening through a 150μm sieve. The angle of repose was 28.3°.

Example 4: Polyamide Particulates Coated with 1.0 Wt. % FluorinatedPolymer Nanoparticles. A 2 L Buchi reactor was loaded with PDMS oilhaving a viscosity of 40,000 cSt (blend of 41.5% 30,000 cSt and 58.5%60,000 cSt PDMS oils) and pre-mixed with 1.0 wt. % of the fluorinatedpolymer nanoparticles prepared as above. Polyamide-12 pellets (RTP,Winona, Minn.) were then added at 30 wt. % relative to the PDMS oil. Thereactor was stirred at 200 rpm under N₂ purge for 10 minutes and thenheated to 250° C. at a rate of 3.6° C./min. The stirring rate wasincreased to 650 rpm when the temperature reached around 230° C. Themelt dispersion was mixed at 650 rpm for an additional 60 minutes afterthe temperature reached 235° C. Heating and N₂ purge were thendiscontinued, and the stirring rate was lowered to 50 rpm. After coolingto room temperature, the slurry was discharged onto a tray. Theresultant polyamide particulates were re-slurred 4 times in heptane andfiltered onto Whatman #1 90 mm filter paper to remove the PDMS oil. Thepolyamide particulates had a D₅₀ of about 58.6 microns (span=0.983)after drying to remove solvent. Two batches of particulates werecombined and screened through a 250 μm sieve for angle of reposemeasurements. The angle of repose was 26.2°. FIG. 4 is a scanningelectron microscope image of the polyamide particulates prepared inaccordance with Example 4. FIG. 5 is a graph showing the particle sizedistribution of the polymide particulates prepared in accordance withExample 4.

The combined batch of powder particulates were then used for SLSprinting using a Snow White printer. Good printing performance wasdemonstrated in a single layer by sintering at a 138° C. temperature setpoint and 40% laser power.

Example 5: Polyamide Particulates Coated with 1.5 Wt. % FluorinatedPolymer Nanoparticles. Example 4 was repeated except, 1.5 wt. % offluorinated polymer nanoparticles were used during melt emulsification,and the PDMS oil had a viscosity of 30,000 cSt. The resultant polyamideparticulates had a D₅₀ of 45.1 microns (span=1.59) after drying toremove solvent and screening through a 150 μm sieve. The angle of reposewas 27.6°.

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents and/or testing procedures to the extent they arenot inconsistent with this text. As is apparent from the foregoinggeneral description and the specific embodiments, while forms of thedisclosure have been illustrated and described, various modificationscan be made without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the disclosure belimited thereby. For example, the compositions described herein may befree of any component, or composition not expressly recited or disclosedherein. Any method may lack any step not recited or disclosed herein.Likewise, the term “comprising” is considered synonymous with the term“including.” Whenever a method, composition, element or group ofelements is preceded with the transitional phrase “comprising,” it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of,” “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,and so forth used in the present specification and associated claims areto be understood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that may vary depending upon the desired propertiessought to be obtained by the embodiments of the present invention. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claim, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

Whenever a numerical range with a lower limit and an upper limit isdisclosed, any number and any included range falling within the range isspecifically disclosed. In particular, every range of values (of theform, “from about a to about b,” or, equivalently, “from approximately ato b,” or, equivalently, “from approximately a-b”) disclosed herein isto be understood to set forth every number and range encompassed withinthe broader range of values. Also, the terms in the claims have theirplain, ordinary meaning unless otherwise explicitly and clearly definedby the patentee. Moreover, the indefinite articles “a” or “an,” as usedin the claims, are defined herein to mean one or more than one of theelement that it introduces.

One or more illustrative embodiments are presented herein. Not allfeatures of a physical implementation are described or shown in thisapplication for the sake of clarity. It is understood that in thedevelopment of a physical embodiment of the present disclosure, numerousimplementation-specific decisions must be made to achieve thedeveloper's goals, such as compliance with system-related,business-related, government-related and other constraints, which varyby implementation and from time to time. While a developer's effortsmight be time-consuming, such efforts would be, nevertheless, a routineundertaking for one of ordinary skill in the art and having benefit ofthis disclosure.

Therefore, the present disclosure is well adapted to attain the ends andadvantages mentioned as well as those that are inherent therein. Theparticular embodiments disclosed above are illustrative only, as thepresent disclosure may be modified and practiced in different butequivalent manners apparent to one having ordinary skill in the art andhaving the benefit of the teachings herein. Furthermore, no limitationsare intended to the details of construction or design herein shown,other than as described in the claims below. It is therefore evidentthat the particular illustrative embodiments disclosed above may bealtered, combined, or modified and all such variations are consideredwithin the scope and spirit of the present disclosure. The embodimentsillustratively disclosed herein suitably may be practiced in the absenceof any element that is not specifically disclosed herein and/or anyoptional element disclosed herein.

The invention claimed is:
 1. A particulate composition comprising: aplurality of thermoplastic particulates comprising a thermoplasticpolymer, and a plurality of polymer nanoparticles disposed upon an outersurface of the thermoplastic particulates, the polymer nanoparticlescomprising a crosslinked fluorinated polymer.
 2. The particulatecomposition of claim 1, wherein the crosslinked fluorinated polymercomprises a fluorinated (meth)acrylic monomer and a divinyl crosslinker.3. The particulate composition of claim 2, wherein the fluorinated(meth)acrylic monomer comprises 2,2,2-trifluoroethyl (meth)acrylate andthe divinyl crosslinker comprises a divinylbenzene.
 4. The particulatecomposition of claim 2, wherein the crosslinked fluorinated polymerfurther comprises an ethylenically unsaturated co-monomer differing fromthe fluorinated (meth)acrylic monomer.
 5. The particulate composition ofclaim 1, further comprising: inorganic nanoparticles disposed upon theouter surface of the thermoplastic particulates, the inorganicnanoparticles comprising a plurality of oxide nanoparticles, carbonblack, or any combination thereof.
 6. The particulate composition ofclaim 5, wherein the oxide nanoparticles comprise silica nanoparticles.7. The particulate composition of claim 1, wherein the thermoplasticparticulates comprise about 0.01 wt. % to about 10 wt. % polymernanoparticles, as measured relative to the thermoplastic polymer.
 8. Theparticulate composition of claim 1, wherein the thermoplasticparticulates are substantially spherical and have a D₅₀ ranging fromabout 1 μm to about 1,000 μm.
 9. The particulate composition of claim 1,wherein the polymer nanoparticles range from about 5 nm to about 500 nmin size.
 10. A method comprising: providing the particulate compositionof claim 1; depositing the particulate composition layer-by-layer in apowder bed; and heating a portion of the powder bed to consolidate aportion of the thermoplastic particulates into a consolidated parthaving a specified shape.
 11. The method of claim 10, wherein heatingtakes place by selective laser sintering.
 12. The method of claim 10,wherein the polymer nanoparticles remain associated with theconsolidated part.
 13. A consolidated part prepared by the method ofclaim 10, the consolidated part comprising: a thermoplastic matrixformed by consolidation of thermoplastic particulates; and polymernanoparticles admixed with the thermoplastic matrix.
 14. A methodcomprising: combining a thermoplastic polymer and polymer nanoparticleswith a carrier fluid at a heating temperature at or above a meltingpoint or softening temperature of the thermoplastic polymer and below amelting point, softening temperature or decomposition temperature of thepolymer nanoparticles; wherein the thermoplastic polymer and the polymernanoparticles are immiscible in the carrier fluid at the heatingtemperature, and the polymer nanoparticles comprise a crosslinkedfluorinated polymer; applying shear to disperse the thermoplasticpolymer as liquefied droplets in the carrier fluid at the heatingtemperature in the presence of the polymer nanoparticles; afterliquefied droplets have formed, cooling the carrier fluid to at least atemperature at which thermoplastic particulates in a solidified stateform, the thermoplastic particulates comprising the thermoplasticpolymer and at least a portion of the polymer nanoparticles disposedupon an outer surface of the thermoplastic particulates; and separatingthe thermoplastic particulates from the carrier fluid.
 15. The method ofclaim 14, wherein the crosslinked fluorinated polymer comprises afluorinated (meth)acrylic monomer and a divinyl crosslinker.
 16. Themethod of claim 15, wherein the fluorinated (meth)acrylic monomercomprises 2,2,2-trifluoroethyl (meth)acrylate and the divinylcrosslinker comprises a divinylbenzene.
 17. The method of claim 15,wherein the crosslinked fluorinated polymer further comprises anethylenically unsaturated co-monomer differing from the fluorinated(meth)acrylic monomer.
 18. The method of claim 14, further comprising:combining inorganic nanoparticles with the carrier fluid, the inorganicnanoparticles comprising a plurality of oxide nanoparticles, carbonblack, or any combination thereof; wherein at least a portion of theinorganic nanoparticles are disposed upon the outer surface of thethermoplastic particulates.
 19. The method of claim 18, wherein theoxide nanoparticles comprise silica nanoparticles.
 20. The method ofclaim 14, wherein the thermoplastic particulates comprise about 0.01 wt.% to about 10 wt. % polymer nanoparticles, as measured relative to thethermoplastic polymer.